Unsaturated polyester resin composition containing indan carboxylic acids and process of preparing the same



United. States Patent:

UNSATURATED POLYESTER RESIN COMPOSI- TION CONTAINING INDAN CARBOXYLICAND PROCESS OF PREPARING THE John C. Petropoulos, South Norwalk, Conn.,assignor. to American Cynnamid Company, New York, N. Y., a corporationof Maine No Drawing. Application February 11, 1955 Serial No. 487,710

20 Claims. (Cl. 260-454) zable group CH,='C wherein the polyester resinis" prepared by reacting a polyhydric alcohol with an alpha, betaunsaturated polycarboxylic acid and a polycarboxylic acid having theformula:

CE: /R O H0 00 11B:

COOH

wherein R is an alltyl group :containing 1 to 4- carbon atoms.

One of the objects of the present invention .is to produce polymerizableunsaturated polyester resin compositions, which may be polymerized toform hard, glossy laminates. A further object of. the present inventionis to produce polymerizable unsaturated polyester resin compositionssuch as those set forth hereinabove and in greater detail hereinbelowand to the product thus'produced. These and other objects of the presentinvention will be discussed in greater detail hereinbelow.

This is a continuation-in-part of my earlier filed patent application,having the Serial No. 414,860, filed March 8, 1954, now abandoned,entitled Novel Compositions of Matter and Processes of Preparing Same."This application discloses and claimsthe method of preparing these novelacids and their use in the preparation of alkyd resins.

The starting materials utilized in the preparation of thedicarboxylic'acids of the presentinvention are substituted styreneshaving an alkyl group or a halo group in the alpha position and amethyl. group: on thering. The alkyl group in. thealpha position may 'beanyone of methyl, ethyl, propyl, and butyl. The propyl group may beeither n-propyl or isopropyl and the butyl group may be either n-butyl,isobutyl or tertiary butyl. The methyl groupon the'ringmay be in. eitherthe ortho, meta or para position. Representative of the class of alkylsubstituted styrenes which may be used in the practice of the process ofthe present invention are tip-dimethylstyrene,arm-dimethylstyrene,,P'dllHCflIYlSiYl'iiDC, a-ethyl-o-methylstyrene,a=ethylm.-methylstyrene, a-ethyl-pmethylstyrene,a-propyl-o-methylstyrene, n-propyl-mmethylstyrene,a-propyl-p-methylstyrene, a-butyl o-methylstyrene,.m-butyl-m-methylstyrene, a-butyl-p-methylstyrene and the like. In placeof the alltyl groups containing between 1 and 4 carbon atoms which may'be substituted on the side chain in the a position, one may utilize thehalo substituents such as the chloro, bromo, iodo and fluoro.Representative of this class of compounds are a-chloro-m-methylstyrene,a-bromo-p-methylstyrene, a-iodo-o-me'thylstyrene, u-fluOrO,p-methylstyrene and the like. The methyl substituent onthe ring may bethe sole substituent on the ring or it may be accompanied by othersubstituents such as other alkyl groups, halo groups, such as thosementioned hereinabove, and the like. In order that the process for thepreparation of the dimers utilized in the practice of the process of thepresent invention may be more completely understood, the followingexamples are set forth in which all parts are parts by weight unlessotherwise indicated. These examples are set forth primarily for thepurpose of illustration and any specific enumeration of detail containedtherein should not be interpreted as a limitation on the case except asindicated in the appended claims.

DIMERIZATION OF a, p-DIMETHYLSTYRENE 800 parts of toluene cooled to 5 C.are introduced into a suitable reaction vessel. To'the toluene, there isadded 140 parts of a 95% sulfuric acid. The mixture is stirredthoroughly and maintained at a temperature of about 0-5 C. To the cooledmixture, there is added 260 parts of nap-dimethylstyrene dissolved in200 parts of toluene. /2 hour at 0-5" C. and is then hydrolyzed with 120parts of water. The organic layer, is washed free of acidic material,with water and is distilled to yield 250 parts of 'a colorless oilhaving a boiling point of 142-144 C. at 0.8 mm. This oil solidifies andhas a'melting point of 37-38 C..uncorrected.

DIMERIZATION OF u-ETHYLsp-METHYLSTYRENE To 400 parts of'toluene:at 5'C., there is added slowly 70 parts of 95% sulfuric acid followed by 144parts of a-ethyl p-methylstyrene dissolvedin 100 parts of toluene. Thetemperature is maintained at 0-l0 C. during the entire addition. Theresulting. mixture is allowed to react for /2 hour and then ishydrolyzed with 100 parts of water. The organic material is collected,washed free of acidic material with water and distilled to yield 130parts of a colorlss liquid having a boiling point of 160- 165 C. at 1mm.

DI MERIZATION OF a,META DIMETHYL STYRENE To 200 parts of toluene: at 0-5C., there is added slowly 35 parts of sulfuric acid, 65 parts ofe,mdimethylstyrene dissolved in 50 parts of toluene. The resultingmixture is allowed to react for about Pi hour and is then hydrolyzedwith water. The organic material is collected, washed anddistilled toyield 61 parts of a colorless liquid having a boiling point of 144-148"C. at 1 mni. pressure.

DIMERIZATION OF CRUDE a,p-DIMETHYL STYRENE To 368parts of toluene at 10C., there is added slr wly 50 parts of anhydrous aluminum chloridefollowed by 516 parts of crude (undistilled) cap-dimethylstyrenedissolved in 368 parts of'toluene while maintaining the temperaturebelow 10 C. After aZO-minute reaction time, the mixture is hydrolyzedwith water and the organic layer is collected and dried. The organicmaterialis distilledto give parts of a colorless oil having a boilingpoint of l38-l40 C. at 0.5-l-mm.

DIM ERlZATlON OF a,p-DIMETHYLSTYRENE A mixture of 310 parts of freshlydistilled cop-dimethylstyrene and 2 parts of p-toluene sulfonic acid areheated in a steam bath for about 16 hours and then allowed to react atroom temperature for 2% months, at which time the The resulting mixtureis allowed to react for p-toluene sulfonic acid catalyst is removed bywashing the organic layer with dilute sodium bicarbonate solution.Distillation of the organic layer gave 151 parts of a very light yellowcolored oil having a boiling point of 136140 C. at 1 mm. pressure.

PREPARATION OF 3-(4-CARBOXYPHENYL)-l,l,3- TRIMETHYL-S-INDAN CARBOXYLICACID Into a suitable reaction vessel equipped with thermometer, stirrerand reflux condenser, there is introduced 34 parts of the dimer ofa,p-dimethylstyrene, 57 parts of concentrated nitric acid and 80 partsof water and the mixture is refluxed for 48 hours. The yield, amountingto about 32 parts, was a light tan solid. This product is collected andwashed free of acid with water. 10 parts of this product is dissolved in150 parts of 1 N sodium hydroxide and there is added thereto 10 parts ofpotassium permanganate and the resulting mixture is allowed to refluxfor 36 hour. The mixture is acidified and then treated with sodiumsulfite, in order to reduce the manganese dioxide to manganese sulfate.This gave a yield of 11 parts of a light tan solid which afterrecrystallization from acetic acid became colorless and had a neutralequivalent of 162 and a melting point of 293-4 C. uncorrected.

AnaIysis.Calculated for C H O C, 74.05; H, 6.22; COOI-I, 27.79. Found:C, 73.83; H, 6.23; COOH, 27.73.

PREPARATION OF 3-(4-CARBOXYPI-IENYL)-l,l,3-

TRIMETHYL-S-INDAN CARBOXYLIC ACID Into an autoclave, there is introduced26.4 parts of the dimer of a,p-dimethylstyrene, 66.2 parts ofconcentrated nitric acid and 61 parts of water and the mixture is heatedslowly in the autoclave. At 150 C., an exothermic reaction develops andthe temperature and pressure increased to 190 C. and 1000 p. s. i.,respectively. After about 10 minutes at 190 C., the autoclave is cooledand the product amounting to about 26 parts (80% yield), is collected.The resulting product is a light tan solid having a melting point of278-285 C. and had a neutral equivalent of 164. When this product isrecrystallized from acetic acid, the colored nitration productimpurities are substantially completely removed and the melting point israised to 293- 294 C.

PREPARATION OF 3-( 4-CARBOXYPHENYL) -l ,3-DI- ETHYL- 1 -METI-IYL--INDANCARBOXYLIC ACID A mixture of 14.6 parts of the dimer of a-ethyl,p-methylstyrene, 23 parts of concentrated nitric acid (specific gravity1.42) and 30 parts of water is heated slowly in an autoclave until atemperature of 190l95 C. is reached. The reaction mixture is held atthis temperature for 14 minutes and then allowed to cool to roomtemperature. The product, a light tan solid, having a neutral equivalentof 175-180, is collected in approximately 7580% yield. The product thusproduced may be further purified by recrystallization from glacialacetic acid or methyl isobutyl ketone.

PREPARATION OF 3-(3-CARBOXYPI-IENYL)-l,l,3- TRIMETHYL-G-INDAN CARBOXYLICACID A mixture of 13 parts of the dimer of e,n1-dimethylstyrene, 23parts of concentrated nitric acid (specific gravity 1.42) and 30 partsof water are heated slowly in an autoclave until a temperature of aboutl90l95 C. is reached. The reaction mixture is held at this temperaturefor about 15 minutes and then allowed to cool to room temperature. Theproduct, a light tan solid having a neutral equivalent of about 160-164is collected in an approximate yield of 78-84%. Again this product maybe further purified by recrystallization as in the preceding example.

In the preparation of the polymerizable unsaturated polyester resinouscompositions of my invention, one may use in combination with thepolycarboxylic acids having the following structural formula:

CH1 HOOC OOOH wherein R is an alkyl group containing 1 to 4 carbonatoms, any of the ethylenically alpha,beta unsaturated polycarboxylicacids such as maleic, fumaric, aconitic, itaconic and the like. Thepreferred polycarboxylic acid free of non-benzenoid unsaturation, whichmay be used, is 3-(4-carboxyphenyl)-1,1,3-trimethyl-5-indan carboxylicacid. For the sake of brevity, this acid has been called phenolic acid.In preparing the unsaturated polyester resins, the a1pha,betaunsaturated polycarboxylic acids should be present in an amountapproximating at least 20% by weight of the total weight ofpolycarboxylic acids used and preferably in amounts varying betweenabout 25% and 65% by weight based on the total weight of polycarboxylicacid present. If it is desired to make use of other saturatedpolycarboxylic acids, i. e., those which are free of non-benzenoidunsaturation, one could use such acids as phthalic, malonic, succinic,glutaric, sebacic, adipic, pimelic, suberic, azelaic, tricarballylic,citric, tartaric, malic and the like but in amounts less than a largerproportion of the total amount of polycarboxylic acid free ofnon-benzenoid unsaturation present. Whenever available, the anhydridesof these acids may be used or mixtures of the acids and/or anhydridesmay be used in the preparation of the polyester resin.

As polyhydric alcohols which may be used in the preparation of thepolymerizable unsaturated polyesters of the present invention, it ispreferred that those alcohols containing only two hydroxy groups beused. However, those alcohols containing three hydroxy groups, fourhydroxy groups, or more hydroxy groups may be used in minor amounts.Illustrative examples of the various dihydroxy alcohols that findemployment in my invention are: ethylene glycol, diethylene glycol,propylene glycol, dipropylene glycol, butanediol-l,4, butanediol-l,3,butanediol-1,2, pentanediol-l,4, pentanediol-1,5, hexanediol-1,6, andthe like. Additionally, such polyhydric alcohols as glycerol,pentaerythritol, dipentaerythritol and the like may be used in myinvention.

In the preparation of the polymerizable unsaturated polyesters, one mayuse the polyhydric alcohols and the polycarboxylic acids in a proportionsubstantially equally about mol for mol and preferably an excess ofalcohol approximating 15% above the stoichiometric quantity required forcomplete esterification. If polyhydric alcohols containing more than twohydroxy groups are used, calculation of the molar proportion should bemade on a stoichiometric basis so as to make allowance for theadditional hydroxy groups such as those found in glycerol,pentaerythritol and the like. This is also true when polycarboxylicacids having more than two carboxyl groups are employed. A sufficientquantity of the alcohol and acid should be reacted so as to produce anultimate polyester resinous material having an acid number not greaterthan about 55 and not lower than about 20 and, preferably an acid numberfrom about 35 to 40. The polymerizable unsaturated polyesters areadmixed with a monomeric compound containing the polymerizable CH =Cgroup to give a composition that may be cured to a stable thermosetcondition. One may use about 10 parts by weight of the monomericmaterial to about parts of the unsaturated polyester resin up to about50 parts of the monomeric material .to about 50 parts of thepolymerizable unsaturated polyester resin. The preferred embodiment,however, is to use from about 25 parts of the monomeric material toabout 35 parts of the monomeric material with about 75 parts to about 65parts, respectively, of the polymerizable unsaturated polyester resin.

The monomeric material containing the polymerizable CH =C group has aboiling point of at least 60 C. Among the polymerizable monomericmaterials that may find use in my invention are such as styrene,side-chain alkyl and halo substituted styrenes such as alpha,methylstyrene, alpha chlorostyrene, alpha ethylstyrene and the like oralkyl and halo ring-substituted styrene such as ortho, meta andpara-alkyl styrenes such as o-methylstyrene, p-ethylstyrene,meta-propylstyrene, 2,4-dimethylstyrene, 2,5-diethylstyrene,bromostyrene, chlorostyrene, dichlorostyrene, and the like. Stillfurther, one can make use of the allyl compounds such as diallylphthalate, tetrachloro-diallyl phthalate, allyl alcohol, methallylalcohol, allyl acetate, allyl methacrylate, diallyl carbonate, allyllactate, allyl alpha-hydroxyisobutyrate, allyl trichloro-silane, allylacrylate, diallyl malonate, diallyl oxalate, allyl gluconate, allylmethylguconate, diallyl adipate, diallyl sebacate, diallyl citraconate,the diallyl ester of muconic acid, diallyl itaconate, diallylchlorophthalate, diallyl dichlorosilane, the diallyl ester ofendomethylene tetrahydrophthalic anhydride, the diallyl ester oftetrachloro endomethylene tetrahydrophthalic anhydride, triallyltricarballylate, triallyl aconitate, triallyl cyanurate, triallylcitrate, triallyl phosphate, trimethallyl phosphate, tetraallyl silane,tetraallyl silicate, hexallyl disiloxane and the like. These monomericmaterials may be used either singly or in combination with one another.

In order that the present invention may be more completely understood,the following examples are set forth in which all parts are parts byweight. These examples are set forth primarily for the purpose ofillustration and any specific enumeration of details set forth thereinshould not be interpreted as limitations on the case except as isindicated in the appended claims.

Example 1 Into a suitable reaction vessel equipped with stirrer,thermometer, inert gas inlet and a steam jacketed condenser, there isintroduced 409 parts of ethylene glycol, 196 parts of maleic anhydrideand 1096 parts of 3-(4- carboxyphenyl)-l,l,3-trimethyl-5-indancarboxylic acid. The charged materials were heated gradually to about190-210" C. while bubbling carbon dioxide through the reaction mass toaid in the removal of water. The temperature of the charge is maintainedat 190 C.2l0 C. until the acid number is 30. The mass is cooled to aboutl50l60 C., whereupon 0.38 part of hydroquinone is added and stirred infor about 5 minutes. The product is then poured into trays to cool. Thepolyester resin thus prepared was a hard, glass-like mass when cooled.

Example 2 700 parts of the polyester resin prepared according to Example1 was dissolved in 300 parts of monomeric styrene. Themixture whenthoroughly dispersed is catalyzed with parts of benzoyl peroxide. Aglass cloth laminate is prepared by successively saturating 12 plies of181 weave glass cloth with the catalyzed resin mix. The laminate iscured by pressing under 30 p. s. i. to a thickness of Va inch for 10minutes at 105 C. The resulting laminate is translucent, tough andrigid. It is capable of withstanding immersion in hot aqueous solutions.

Example 3 .Into a suitable reaction vessel equipped as in Example 1,there is introduced 502 parts of propylene glycol, 294

650 parts of the polyester resin prepared according to Example 3 wasdissolvedin 350 parts of paramethyl styrene. The mixture is catalyzedwith 10 parts of benzoyl peroxide and poured between two glass platesthat are sealed together on three edges by a suitable gasket material.The resinous composition was cured by heating at 60 C. for 3 hoursfollowed by 30 minutes at C. The cast material was clear and rigid andexhibited resistance to aqueous as well as non-aqueous solutions.

Example 5 Example 2 is repeated in which 600 parts of the polyester ofExample 1 is dissolved in a mixture of 200 parts of monomeric styreneand 200 parts of diallyl phthalate.

The mix is catalyzed with 10 parts of tertiary butylhydroperoxide. Aglass cloth laminate is prepared as in Example 2 by successivelysaturating a plurality of plies of glass cloth with the catalyzed resinmix. The laminate is cured by pressing under 50 p. s. i. at C. for 10minutes. The resulting laminate was hard, rigid and capable ofwithstanding immersion in hot aqueous solutions.

Example 6 800 parts of the polyester resin prepared according to Example4 and 200 parts of triallyl cyanurate are blended together to form a.homogeneous mass and there is added thereto 10 parts of methyl ethylketone peroxide and 0.1 part of cobalt naphthenate. The resinouscomposition thus catalyzed was cured by heating at 60 C. for 3 hoursfollowed by 30 minutes at 100 C.

Amongst the polycarboxylic acids which may be used to prepare thepolyester resins of the present invention are3-(4-carboxyphenyl)-l,l,3-trimethyl-5-indan carboxylic acid,3-(4-carboxyphenyl)-l,3-diethyl-l-methyl-S-indan carboxylic acid,3-(4-carb0xyphenyl)-1,3-dipropyll-methyl-S-indan carboxylic acid,3-(4-carboxyphenyl)- l,3-dibutyl-l methyl-5-indan carboxylic acid,3-(3-carboxyphenyl)-1,1,3-trimethyl-6-indan carboxylic acid, 3-(3-carboxyphenyl)-1,3-diethyl-1-methyl-6-indan carboxylic acid,3-(3-carboxyphenyl)-1,3-dipropyl-1-methyl-6- indan carboxylic acid,3-(3-carboxyphenyl)-l,3-d.ibutyl- 1-methyl-6-indan carboxylic acid,3-(4-carboxyphenyl)- l,3-dichloro-I-methyI-S-indan carboxylic acid,3-(4-carboxyphenyl) 1,3 dibromo 1 methyl 5 indan carboxylic acid,3-(4-carboxyphenyl)-1,3-diiodo-1-methyl-5- indan carboxylic acid,3-(3-carboxyphenyl)-l,3-dichlorol-methyl-6-indan carboxylic acid;3-(3-carboxyphenyl)- l,3-dibromo-l-methyl-6-indan carboxylic acid;3-(3-carboxyphenyl)-l,3-diiodo-I-methyLG-indan carboxylic acid; 3 (2carboxyphenyl) 1,1,3 trimethyl 7 indan c rboxylic acid;3-(Z-carboxyphenyl)-1,3-diethyl-l-methyl-7 indan carboxylic acid;3-(2-carboxyphenyl)-1,3-dipropyll-methyl-7- indan carboxylic acid;3-(2-carboxyphenyl)- 1,B-dibutyl-l-methyl-7-indan carboxylic acid;3-(2-carboxyphenyl) 1,3 dichloro 1 methyl 7 indan car boxylic acid;3-(2-carboxyphenyl)-l,3-dibromo-l-methyl- 7-indan carboxylic acid;3-(Z-carboxyphenyl)-l,3-diiodol-methyl-7-indan carboxylic acid and thelike. Obviously, these acids may be used either singly or in combinationwith one another.

In the preparation of the unsaturated polyester resins of the presentinvention, it is unnecessary to use a catalytic material as the acidsand the dihydric alcohols will readily react at elevated temperatures toproduce the polyester resin. When the unsaturated polyester resin iscombined with the polymerizable monomeric material, however, it isdesirable to incorporate therein a polymerization inhibitor in order toprevent premature gelation of the resinous composition, particularly ifit is expected that said composition will be subjected to prolongedperiods of storage or if it is expected that it will be subjected totemperatures significantly higher than room temperature. With thepolymerization inhibitor, the resinous composition will remain stable atroom temperature for months without noticeable deterioration. Amongstthe polymerization inhibitors which may be used are any of those whichare conventionally known and used in the art such as hydroquinone,benzaldehyde, ascorbic acid, isoascorbic acid, resorcinol, tannin,symmetrical di-(betanaphthyl)-p-phenylene diamine, phenolic resins,sulfur resins and the like. The concentration of the inhibitor ispreferable and as a general rule less than about 1% by weight is usuallysuificient. However, with the preferred inhibitors, e. g., polyhydricphenols and aromatic amines, one may make use of such small amounts as0.0l%0.1% by weight.

The unsaturated polyester resins of the present invention will findapplication in a great plurality of fields such as in the preparation oflaminates and other reinforced plastics, coating compositions. adhesivecompositions, molding compositions, potting and the like. Thesepolyester resins can readily be solidified without benefit of catalystby the application of heat or by the application of heat and pressure.However, in such an operation without benefit of a catalytic agent thetime element makes it desirable to incorporate into the compositionconventional polymerization catalysts such as the organic superoxides,the alcoholic and acidic peroxides. Among the preferred catalysts are:the acidic peroxides, e. g., benzoyl peroxide, phthalic peroxide,succinic peroxide and benzoyl acetic peroxide; fatty oil acid peroxides,e. g., coconut oil acid peroxides, lauric peroxide, stearic peroxide andoleic peroxide; alcohol peroxides, e. g., tertiarybutyl hydroperoxide,usually called tertiary-butyl peroxide and terpene oxides, e. g.,ascaridole. Still other polymerization catalysts might be used in someinstances, e. g., soluble cobalt salts (particularly the linoleate andnaphthenate). p-toluene sulfonic acid, aluminum chloride, stannicchloride and boron trifiuoride.

The compositions of the present invention may be used alone or inadmixture with a filler or a dye, pigment, opacifier. lubricant and thelike. Among the fillers which may be employed are alpha cellulose pulp,asbestos fibers, cotton flock, chopped cloth cuttings, glass fibers,wood llour, mica dust, sand, clay, diatomaccous earth and the like.

Natural or other synthetic resins and other modifiers may beincorporated into the unsaturated polyester resinous compositions ofthis invention in order to modify the latter and to obtain productswhich may be especially suited for a particular service application.Examples of such modifying agents are shellac, ester gums. celluloseesters and others, urea-aldehyde resins. aminotriazinealdehyde resins(e. g. melamine-formaldehyde resins), phenol-aldehyde resins.hydrocarbon-substituted polysiloxane resins, e. g.. methyl polysiloxaneresins, methyl phenyl polysiloxane resins, phenyl polysiloxane resins,conventional alkyd resins of the nonpolymerizable type, etc. Thepolymers and copolymers of this invention also may be modified byincorporating therewith rubber or synthetic rubber-like products.

If it is desired, one may use a promoter in combination with thecatalytic agent in order to accelerate the cure of the polymerizablepolyester resin composition to a thermoset state. Amongst the promoterswhich may be utilized are those disclosed in the U. S. Patents 2,466,800and 2,480,928. Particularly advantageous are the mercaptans such asn-hexyl mercaptan, n-heptyl mercaptan, n-octyl mercaptan, n-nonylmercaptan, ndecyl mercaptan, n-undecyl mercaptan, n-dodecyl mercaptan,n-tridecyl mercaptan, n-tetradecyl mercaptan, n-hexaclecyl mercaptan,secondary hexyl mercaptan, tertiary hexyl mercaptan, tertiary octylmercaptan, and the like. The dialkyl substituted anilines areadditionaly useful as promoters, particularly the dimethyl aniline,diethyl aniline, dipropyl aniline, dibutyl aniline and the like.Obviously, these promoters can be used either singly or in combinationwith one another.

I claim:

1. A process for preparing an unsaturated polyester resin compositioncomprising heat reacting an unsaturated polyester resin with apolymerizable compound containing a CH =C group, wherein said polyesterresin is the reaction product of a polyhydric alcohol, an alpha, betaethylenically unsaturated polycarboxylic acid and an acid having theformula:

s i CH:

HOOC

wherein R is an alkyl group containing 1 to 4 carbon atoms.

3. A process for preparing an unsaturated polyester resin compositioncomprising heat reacting an unsaturated polyester resin with styrene,wherein said polyester resin is the reaction product of a polyhydricalcohol, an alpha, beta ethylenically unsaturated polycarboxylic acidand an acid having the formula:

HOOC

t dl-R HOOC wherein R is an alkyl group containing 1 to 4 carbon atoms.

4. A process for preparing an unsaturated polyester resin compositioncomprising heat reacting an unsaturated polyester resin with diallylphthalate, wherein said polyester resin is the reaction product of apolyhydric alcohol, an alpha,beta ethylenically unsaturatedpolycarboxylic acid and an acid having the formula:

HOOC

(IJOOH wherein R is an alkyl group containing 1 to 4 carbon atoms.

5. A process for preparing an unsaturated polyester resin compositioncomprising heat reacting an unsaturated polyester resin with triallylcyanurate, wherein said polyester resin is the reaction product'of apolyhydric alcohol, an alpha,beta ethylenically unsaturatedpolycarboxylic acid and an acid having the formula:

3 T on, 13000 (I:

COOH

wherein R is an alkyl group containing 1 to 4 carbon atoms.

6. A process for preparing an unsaturated polyester resin compositioncomprising heat reacting an unsaturated polyester resin with apolymerizable compound containing a CH =C group, wherein said polyesterresin is the reaction product of a polyhydric alcohol, an alpha, betaethylenically unsaturated polycarboxylic acid and 3- (4 carboxyphenyl)1.1.3 trimethyl-S-indan carboxylic acid.

7. Aprocess for preparing an unsaturated polyester resin compositioncomprising heat reacting an unsaturated polyester resin with a styrene,wherein said polyester resin is the reaction product of a polyhydricalcohol, an alpha, beta ethylenically unsaturated polycarboxylic acidand 3-(4-carboxyphenyl)-l,l,3-trimethyl 5 indan carboxylic acid.

8. A process for preparing an unsaturated polyester resin compositioncomprising heat reacting an unsaturated polyester resin with styrene,wherein said polyester resin is the reaction product of a polyhydricalcohol, an alpha, beta ethylenically unsaturated polycarboxylic acidand 3-(4-carboxyphenyl -l,l,3-trimethyl-5-indan carboxylic acid.

9. A process for preparing an unsaturated polyester resin compositioncomprising heat reacting an unsaturated polyester resin with diallylphthalate, wherein said polyester resin is the reaction product of apolyhydric alcohol, an alpha,beta ethylenically unsaturatedpolycarboxylic acid and 3-(4-carboxyphenyl)-l,l,3-trimethyl- S'indancarboxylic acid.

10. A process for preparing an unsaturated polyester resin compositioncomprising heat reacting an unsaturated polyester resin with triallylcyanurate, wherein said polyester resin is the reaction product of apolyhydric cm a l. L.

I coon wherein R is an alkyl group containing 1 to 4 carbon atoms.

12. A composition of matter comprising a polymerizable mixture of anunsaturated polyester resin and a styrene, wherein said polyester resinis the reaction product of a polyhydric alcohol, an alpha,betaethylenically unsaturated polycarboxylic acid and an acid having theformula:

HOOC

wherein R is an alkyl group containing 1 to 4 carbon atoms.

13. A composition of matter comprising a polymerizable mixture of anunsaturated polyester resin and styrene, wherein said polyester resin isthe reaction product of a polyhydric alcohol, an alpha,betaethylenically unsaturated polycarboxylic acid and an acid having theformula:

HOOC

wherein R.is an alkyl group containing 1 to 4 carbon atoms.

14. A composition of matter comprising a polymerizable mixture of anunsaturated polyester resin and diallyl phthalate, wherein saidpolyester resin is the reaction product of a polyhydric alcohol, analpha,beta

a 12 ethylenically unsaturated polycarboxylic acid and an acid 16. Acomposition of matter comprising a polymerhaving the formula: izablemixture of an unsaturated polyester resin and a CH3 R polymerizablecompound containing a CH =C group wherein said polyester resin is thereaction product of a polyhydric alcohol, an alpha,beta ethylenicallyunsaturated polycarboxylic acid and 3-(4-carboxyphenyl)-l,1,3-trimethyl-S-indan carboxylic acid.

17. A composition of matter comprising a polymerizable mixture of anunsaturated polyester resin and a styrene wherein said polyester resinis the reaction product of a polyhydric alcohol, an alpha,betaethylenically unsaturated polycarboxylic acid and 3-(4-carboxyphenyl)-1,1,3-trimethyl-5-indan carboxylic acid. I 18. A composition of mattercomprising a polymer- COOH l5 izable m1xture of an unsaturated polyesterresln and wherein R is an alkyl group containing 1 to 4 carb styrenewherein said polyester resin is the reaction product atoms. of apolyhydric alcohol, an alpha,beta ethylenically un- IS. A composition ofmatter comprising a polymersatulaid p y t y acid 2 YP 3 izable mixtureof an unsaturated polyester resin and 1,1.3-tr1methy cafboxyllcacldtriallyl cyanurate, wherein said polyester resin is the AComposition of matte! comprising a P y reaction product of n polyhydricl oh l, an l h b t izable mixture of an unsaturated polyester resin andethylenically unsaturated polycarboxylic acid and an acid diallylPhthalate wherein Said Polyester resin is the having the formula: tionproduct of a polyhydric alcohol, an alpha,beta ethylenically unsaturatedpolycarboxylic acid and 3-(4-carboxyphenyl)-1,l,3-trimethyl-5-indancarboxylic acid.

20. A composition of matter comprising a polymerizable mixture of anunsaturated polyester resin and triallyl cyanurate, wherein saidpolyester resin is the reaction product of a polyhydric alcohol, analphabeta ethylcnically unsaturated polycarboxylic acid and3-(4-carboxyphenyl)-l,l,3-trimethyl-5-indan carboxylic acid.

HOOC

References Cited in the file of this patent UNITED STATES PATENTS (100112.255313 Ellis Sept. 9, 1941 wherein R is an alkyl group containing 1 to4 carbon. OTHER REFERENCES atoms. Beilstein First Supplement, volume 9,page 417, 1932.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION.

Patent No. 2,830,966 April 15, 1958 John C. Petropoulos It is herebycertified that error appears in the printed specification of the abovenumbered patent requiring correction and that the said Letters Patentshould read as corrected below.

Column 2, line 44, for "colorlss" read colorless column 4, line 23, for"phenolic acid" read phendic acid column 5, line 25,

for "methylguconate read methylgluconate column 10, line 1, for"unaturated" read unsaturated Signed and sealed this 9th day ofSeptember 1958.

SEAL) ttest:

KARL H. AXLINE ROBERT c. WATSON Attesting Oflicer Commissioner ofPatents

1. A PROCESS FOR PREPARIG AN UNSATURATED POLYESTER RESIN COMPOSITIONCOMPRISING HEAT REACTING AN UNSATURATED POLYESTER RESIN WITH APOLYMERIZABLE COMPOUND CONTAINING A CH2=C< GROUP, WHEREIN SAID POLYESTERRESIN IS THE REACTION PRODUCT OF A POLYHYDRIC ALCOHOL, AN ALPHA, BETAETHYLENCIALLY UNSATURATED POLYCARBOXYLIC ACID AND AN ACID HAVING THEFORMULA: